In this work we investigate, to what extent the experimental measurement of the molecular beam deflection of isolated clusters in an inhomogeneouse electric field can be used to determine their geometrical structure. The molecular beam deflection is connected to the Stark effect of the particles and therefore with their permanent dipole moment and electric polarizability. By comparing the thus measured dipole moments and polarizabilities, it is in principle possible to extract experimental, structural information. This approach is demonstrated on small barium species, GeN-, SnN and PbN clusters as well as bimetallic MgMPbN clusters. Is is shown, that the experimental results can be interpreted in agreement with quanten chemical calculation, as long as the investigated species are sufficiently rigid.